title: A direct stereoselective preparation of a fish pheromone and application of the zinc porphyrin tweezer chiroptical protocol in its stereochemical assignment.
abstract: A two-step stereoselective preparation of a goldfish pheromone, 17α,20β-dihydroxy-4-pregnen-3-one, is reported from the readily available cortexolone in 64% overall yield. The (20S)-epimer was also synthesized in three steps from cortexolone with an overall yield of 47%. A microscale chiroptical technique based on a host/guest complexation mechanism between the substrate and a dimeric metalloporphyrin host (tweezer) was used to confirm the stereochemical assignment, while Density Functional Theory (DFT) calculations were employed to explain the high stereoselectivity induced by the 17α-hydroxyl and C18-methyl groups.
authors.affiliation: Department of Chemistry, Florida Institute of Technology, Melbourne, Florida 32901, USA.
authors.forename: Yannick P
authors.initials: YP
authors.lastname: Ouedraogo
authors.forename: Longchuan
authors.initials: L
authors.lastname: Huang
authors.forename: Mariana P
authors.initials: MP
authors.lastname: Torrente
authors.forename: Gloria
authors.initials: G
authors.lastname: Proni
authors.forename: Ekaterina
authors.initials: E
authors.lastname: Chadwick
authors.forename: Rudolf J
authors.initials: RJ
authors.lastname: Wehmschulte
authors.forename: Nasri
authors.initials: N
authors.lastname: Nesnas
mesh_terms: D000818:Animals; D002942:Circular Dichroism; D006054:Goldfish; D006908:Hydroxyprogesterones / Q000138:chemical synthesis* / Q000737:chemistry; D008665:Metalloporphyrins / Q000737:chemistry*; D015394:Molecular Structure; D052898:Optical Tweezers; D055095:Optics and Photonics / Q000295:instrumentation / Q000379:methods; D010675:Pheromones / Q000138:chemical synthesis / Q000737:chemistry*; D011789:Quantum Theory; D013237:Stereoisomerism
chemical_list: D006908:Hydroxyprogesterones; D008665:Metalloporphyrins; D010675:Pheromones; C007433:17,20-dihydroxy-4-pregnen-3-one; C017802:zinc hematoporphyrin
keywords: DFT; circular dichroism; computational modeling; cortexolone; goldfish pheromone; stereoselective reduction; zinc porphyrin tweezer